Benzoheterocyclic compounds

ABSTRACT

Novel hydroxy-benzoheterocyclic-substituted 3-oxopentane derivatives are produced by reaction of a hydroxy-containing ortho-phenylene amine compound and the source of a five-carbon keto-containing moiety selected from 4-oxoheptanedioic acid compounds or 1,6-dioxa[4,4]spirodilactones. The derivatives produced from hydroxy-phenylenediamines are further reacted to produce compounds of higher cyclic functionality. The products are bisphenols which are precursors of thermoplastic and thermoset polymers of high melting point or glass transition temperature which are useful in high temperature applications.

This is a division of application Ser. No. 351,509 filed May 15, 1989,now abandoned.

FIELD OF THE INVENTION

This invention relates to certain novel hydroxy-containingbenzoheterocyclic compounds and to processes for the production thereof.More particularly, the invention relates to the products of the reactionof a hydroxy-containing ortho-phenylene amine compound with a4-oxoheptanedioic acid compound or a 1,6-diaza[4.4]spirodilactone andcyclized derivatives of certain such products.

BACKGROUND OF THE INVENTION

The class of aromatic bisphenols is well known in the art. A commercialexample of such a compound is 2,2-di-(4-hydroxyphenyl)propane, alsoknown as bisphenol A or BPA. The bisphenols are particularly useful asmonomeric precursors of polymers of a variety of types. Reaction of abisphenol with a haloepoxyalkane, e.g., epichlorohydrin, results in theproduction of the corresponding glycicyloxy derivative which reacts witha number of conventional curing agents to produce thermoset resinshaving good properties of strength and rigidity. The allyloxy orproparglyloxy derivatives of the bisphenols are also curable to producethermoset resins. Alternatively, reaction of an alkali metal salt of thebisphenol with a di(halophenyl) sulfone or a di(halophenyl) ketoneresults in the production of thermoplastic polymers of the phenoxy type.

Bisphenols containing additional cyclic structures are particularlydesirable when polymers to be employed in high temperature applicationsare desired. Such bisphenols are precursors of polymers, boththermoplastic and thermoset, which frequently have relatively highmelting points of glass transition temperatures. These polymers findparticular utility when dimensional stability is required for a polymerlikely to be exposed to elevated temperatures. It would be of advantageto provide novel bisphenols having a plurality of types of cyclicstructure within the bisphenol molecule.

SUMMARY OF THE INVENTION

The present invention relates to novel heterocyclic bisphenols as wellas to the process for the production thereof. More particularly, theinvention relates to the reaction of, and reaction productions derivedtherefrom, a hydroxy-containing ortho-phenylene amine compound and asource of a five-carbon keto-containing moiety, which source is selectedfrom a 4-oxoheptandioic acid compound of a 1,6-dioxa[4.4]spirodilactone.

DESCRIPTION OF THE INVENTION

The novel compounds of the invention are characterized by the presenceof two hydroxy-substituted benzoheterocyclic moieties. In onemodification of the compounds of the invention, the hydroxy-substitutedbenzoheterocyclic moieties are connected by a five-carbon connectinggroup having a carbonyl group, i.e., a keto group, in the center of 3position. The source of this five-carbon keto-containing group, i.e., aketo-C₃ group, is a 4-oxoheptanedioic acid compound or a 1,6-dioxa [4.4]spirodilactone. The products in this modification of the compounds ofthe invention are 1,5-di(benzoheterocyclic)-3-oxopentane compounds. In asecond modification of the compounds of the invention, certain of theheterocyclic 3-oxopentane products undergo internal dehydration toproduce of greater cyclic functionality.

In one embodiment of the process of the invention, the keto-C₅ source isa ketodicarboxylic acid compound having two carbon atoms between theketo group and each carboxy function. Expressed in other terms, theketo-C₅ is a 4-oxoheptanedioic acid compound. Although a variety of such4-oxoheptanedioic acid compounds having a variety of substituents inaddition to the keto group and the carboxy functions, the preferred4-oxoheptanedioic acid compounds have up to 30 carbon atoms and arerepresented by the formula ##STR1## wherein A independently is hydroxy,alkoxy, preferably lower alkoxy of up to 4 carbon atoms, or halo,preferably the middle halogens chloro or bromo. The term Z independentlyis >C(Z')₂ in which Z' independently is hydrogen, lower alkyl,preferably methyl, halo, preferably the lower halogens fluoro or chloro,or aryl, preferably phenyl, or Z is such that two adjacent Z groupstaken together form a ring system Z" of from 5 to 7 ring atoms up to twoof which are heteroatoms selected from nitrogen, oxygen or sulfur withthe remainder of the ring atoms being carbon atoms, there being up to 15carbon atoms in each Z", two of which form a bridge between the carbonatoms connected by the adjacent by the adjacent Z groups. When adjacentZ groups are Z", the ring system is aromatic, cycloaliphatic orheterocyclic and is otherwise hydrocarbyl containing only atoms ofcarbon and hydrogen besides any heteroatoms or is substitutedhydrocarbyl containing additional atoms in the form of inert, carbonatom substituents, e.g., halogen atoms, preferably middle halogen atoms.

In a first aspect of the use of the ketodiacid compounds as a keto-C₅source, each Z is not part of a fused ring system and is thereforeacyclic, i.e., each Z is >C(Z')₂ and the ketodicarboxylic acid is anacyclic 4-oxoheptanedioic acid compound. Such 4-oxoheptanedioic acidcompounds are represented by the formula ##STR2## wherein Z' and A havethe previously stated meanings. These acid compounds are illustrated by4-oxoheptanedioic acid, dimethyl 4-oxoheptanedioate,3,5-diphenyl-4-oxoheptanedioic acid,2,3,5,6-tetramethyl-4-oxoheptanedioyl chloride,di-n-propyl-2,6-di-n-butyl-4-oxoheptanedioate,3-methyl-4-oxoheptanedioic acid and 6-carbomethoxyhexanoic acid. Thepreferred compounds of the above formula Ia are those wherein each Z' ispreferably hydrogen or methyl, expecially hydrogen, and each A ishydroxy or alkoxy, particularly hydroxy.

The ketodicarboxylic acids of formula Ia are known compounds or areproduced by known methods but certain of the esters of formula Ia, i.e.,the compounds wherein A is alkoxy, are conveniently produced by thereaction of formaldehyde with an unsaturated carboxylic acid ester suchas methyl acrylate, ethyl methacrylate, methyl crotonate and propyl2,3-dimethyl-2-butenoate. This reaction, conducted in the presence of athiazolium compound and a tertiary amine as a catalyst system, producesthe 4-oxoheptanedioate derivatives in good yield. The process isdescribed in more detail and claimed in U.S. Pat. No. 4,800,231. Theconversion of the esters thereby obtained to the corresponding acids oracid halides is by conventional methods.

In a second aspect of the use of a ketodicarboxylic acid compound as aketo-C₅ source, the ketodiacid incorporates fused cyclic substituentsbetween the keto group and the carboxy group and the carboxy functions,i.e., the two adjacent Z moieties form a cyclic ring system Z". Suchdiacid compounds are represented by the formula ##STR3## wherein Z" hasthe previously stated meaning. Illustrative of these cyclic ketodiacidcompounds are di-2-carboxyphenyl) ketone, di(2-carboxycyclohexyl)ketone, di(2-chlorocarbonylphenyl) ketone, di(2-carboxypyridyl) ketone,2-carboxyphenyl N-methyl-3-carboxy-2-pyrrl ketone,di(3-carboxy-2-morpholyl) ketone and di(2-carbethoxyphenyl) ketone. Thepreferred compounds of formula Ib are those wherein each Z" is a ringsystem of from 5 to 6 ring atoms including up to one nitrogen atom,preferably a ring system of 6 carbon atoms. The cyclic 4-oxoheptanedioicacid compounds of formula Ib are known compounds or are produced byknown methods, for example, the process of Conover et al, U.S. Pat. No.1,999,181, or the method of Cava et al, J. Am. Chem. Soc, 20, 6022(1955).

In yet another aspect of the use of the 4-oxoheptanedioic acid compoundas the keto-C₅ source, the ketodiacid incorporates one fused ringsubstituent with the remainder of the Z groups being acyclic, i.e., thecompounds represented by the formula ##STR4## wherein A, Z' and Z" havethe previously stated meaning. Such ketodiacid compounds of one cyclicfused ring substituent are exemplified by 3-(2-carboxybenzoyl)propionicacid, 3-(3-carbomethoxy-2-pyridyloyl)-2-ethylpropionic acid, ethyl3-(2-carboxybenzoyl)propionate and3-(2-carboxy-4methylbenzoyl)propionate. The ketoacid compounds offormula Ic are known compounds or are produced by known methods. Forexample, 2-carbomethoxybenzaldehyde reacts with methyl acrylateaccording to the general teachings of copending U.S. Pat. No. 4,800,231,filed Mar. 23, 1988.

In a second embodiment of the hydroxy-containing ortho-phenylene aminecompound reacting with a keto-C₅ source, the keto-C₅ source is a1,6-dioxa[4.4]spirodilactone in which the spiro ring system issubstituted with a variety of monovalent of fused ring substitutents.One class of such [4.4]spirodilactones is represented by the formula##STR5## wherein Z has the previously stated meaning.

In one aspect of the use of these spirodilactones as the keto-C₅ source,each Z is acyclic, i.e., each Z is >C(Z')₂ and the spirodilactonecompounds are represented by the formula ##STR6## wherein Z' has thepreviously states meaning. Illustrative of such spirodilactones are1,6-dioxaspiro[4.4]nonane-2,7-dione,3,8-dimethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,4,8,9-tetramethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione,4,9-diphenyl-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,3,4,4,8,8,9,9-octamethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione and3,4,8, 9-tetrafluoro-1,6-dioxaspiro[4.4]nonane-2,7-dione. The preferredspirodilactones of the above formula IIa are those wherein at least oneZ' of each Z'-substituted carbon atom is hydrogen. The compounds offormula IIa are known compounds or are produced by known methods, e.g.,the process of Pariza et al, Synthetic Communications, Vol. 13(3), pp.243-254 (1983).

In a second aspect of the use of spirodilactones as the keto-C₅ source,a cyclic, fused ring substituent is present on each of the two spirorings, i.e., adjacent Z groups are Z". Such spirodilactones arerepresented by the formula ##STR7## wherein Z" has the previously statedmeaning. The spirodilactones of this class are illustrated by3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,4,8,9-di(cyclopentano)-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,4,8,9-di-4-methylbenzo)-1,6-dioxaspiro[4.4]nonane-2,7-dione and3,4,8,9-di(pyrido)-1,6-dioxaspiro[4.4]nonane-2,7-dione. These compoundsare known compounds or are produced by known methods, for example, theprocess of the above Cava et al article or by the process of U.S. Pat.No. 1,999,181.

In a third aspect of the use of spirodilactones as the keto-C₅ source, acyclic substituent is fused to one spiro ring and the other spiro ringis free of fused cyclic substituents, e.g., spirodilactones of theformula ##STR8## wherein Z' and Z" have the previously stated meanings.Such spirodilactones are illustrated by3,4-benzo-8-methyl-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,4-pyrido-1,6-dioxaspiro[4.4]nonane-2,7-dione,3,4-benzo-8,9-diphenyl-1,6-dioxaspiro[4.4]nonane-2,7-dione and3,3,4,4-tetramethyl-8, 9-morpholo-1,6-dioxaspiro[4.4]nonane-2,7-dione.The spirodilactones of formula IIc are known compounds or are producedby known methods, for example, by the dehydration of the correspondingketodicarboxylic acid. By way of specific illustration,3,4-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione is produced by dehydrationof 3-(2-carboxybenzoyl)propionic acid upon application of heat.

In general, the preferred spirodilactones to be used as a keto-C₅ sourceare hydrocarbon except for the oxygens of the lactone moieties andparticularly preferred are those spirodilactones which are free fromcyclic fused ring substituents (formula IIa) or which have fused ringsubstituent on each of the spiro rings (formula IIb). As especiallypreferred spirodilactone of the former class is1,6-dioxaspiro[4.4]nonane-2,7-dione whereas an especially preferredmember of the latter class is3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione.

The keto-C₅ is reacted in the process of the invention, whether a4-oxoheptanedioic acid compound or a spirodilactone, with ahydroxy-containing ortho-phenylene amine compound. These amine compoundsare organic compound having at least one aromatic ring containing anamino substituent, i.e., a --NH₂ group, and having as a substituent on aring carbon atom adjacent to the carbon atom on which the amino group islocated a second substituent which is amino, alkylamino, hydroxy orthiol. A third substituent, a hydroxy substituent, is located on a ringcarbon atom which is not adjacent to either of the carbon atoms on whichthe amino substituent or the second substituent is located. One class ofsuch hydroxy-containing o-phenylene amine compounds is represented bythe formula ##STR9## wherein Y is amino, alkylamino, hydroxy or thioland R is aromatic of up to 20 carbon atoms and from 1 to 2 aromaticrings, inclusive, having, when two rings are present, rings which arefused or are connected by a direct valence bond, alkylene of up to 8carbon atoms inclusive, oxy, thio, sulfonyl or carbonyl. When R has tworings, it is generally preferred that the third substituent, i.e., thehydroxy group, is located on one aromatic ring and that the amino groupand the second substituent are located on the other ring, although suchis not required. R is otherwise hydrocarbyl containing only atoms ofcarbon and hydrogen in addition to any other atoms present in thedivalent connecting groups, or R is substituted hydrocarbyl containingother atoms present as inert carbon atom substituents, e.g., atoms suchas halogen, preferably middle halogen.

Illustrative of the hydroxy-containing o-phenylene amine compounds are3,4-diaminophenol, 4,5-diamino-3-methyl-phenol,5-hydroxy-2,3-diaminonaphthalene, 3,4-diamino-4'-hydroxybiphenyl,4-(4-hydroxyphenyloxy)-1,2-diaminobenzene,3-(4-hydroxybenzoyl)-1,2-diaminobenzene,4-(4-hydroxyphenyloxy)-2-methylaminoaniline, 4-aminoresorcinol,4-(3-hydroxyphenylthio)-2-aminophenyl,3-hydroxyphenyl-2-aminothiophenol, 2-amino-1,5-dihydroxynaphthalene,3-amino-4-ethylaminophenol,3-(4-hydroxyphenylsulfonyl)-2-aminothiophenol and3-amino-2-propylamino-3'-hydroxybiphenyl. In general, thehydroxy-containing p-phenylenediamines are preferred over thecorresponding hydroxy-containing alkylaminoamines, aminophenols oraminothiophenols. The compound 3,4-diaminophenol is particularlysatisfactory.

The reaction of the keto-C₅ source and the hydroxy-containingo-phenylene amine compound is conducted in the liquid phase underreaction conditions in the presence of an inert reaction diluent.Suitable reaction diluents are liquid under reaction conditions and arepolar diluents capable of dissolving at least a portion of each reactantat reaction temperature. Such diluents include ketones such as methylisobutyl ketone and di-n-propyl ketone, esters such as ethyl2-ethylhexanoate, ethers including acyclic ethers such as diethyleneglycol diethyl ether and tetraethylene glycol dimethyl ether as well ascyclic esters such as tetrahydrofuran and dioxane, N-alkylamides such asN,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone,phenols such as phenol and m-cresol, and sulfur-containing diluents suchas dimethyl sulfoxide and sulfolane. The preferred reaction diluent ism-cresol.

The keto-C₅ source and the hydroxy-containing o-phenylane amine compoundcombine in a molar ratio of 1:2 to produce a heterocyclic bisphenolaccording to the process of the invention. It is satisfactory inpractice to provide the keto-C₅ source and the hydroxy-containingo-phenylene diamine compound in a molar ratio of from about 2:1 to about1:8 and even higher or lower ratios can be used. Molar ratios of fromabout 1:1 to about 1:4 are preferred. Suitable reaction temperatures arefrom about 125° C. to about 250° C., preferably from about 150° C. toabout 225° C., depending in part on the particular reaction diluent tobe employed. The reaction pressure will be sufficient to maintain thereaction mixture in the liquid phase at reaction temperature. Typicalreaction pressures will be up to about 20 atmospheres but more oftenfrom about 0.8 atmospheres to about 10 atmospheres. During reaction, thecontact of the reactants is maintained by conventional methods such asshaking, stirring or refluxing and subsequent to reaction theheterocyclic bisphenol product is recovered by well-known methods suchas extraction, precipitation or solvent removal.

Reaction of the keto-C₅ source and the hydroxy-containing o-phenyleneamine compound results in the production of a hydroxy-substitutedbenzoheterocyclic compound which incorporates one carbon atom of theketo-C₅ source in each of the two heterocyclic ring systems, which ringsystems are connected by the residual five-carbon bridge of the keto-C₅source wherein an oxo group or a keto group is located in the center orthe 3-position of the five-carbon bridge. The benzoheterocyclic productresulting from the reaction of the keto-C₅ source and thehydroxy-containing o-phenylene compound is a benzimidazoyl derivative, abenzoxazoyl derivative or a benzothiazoyl derivative if thehydroxy-containing o-phenylene amine compound is a diamine, anaminophenol or an aminothiophenol, respectively. In terms of the keto-C₅source of either formula I or formula II and the hydroxy-containingo-phenylene amine compounds of formula III, the heterocyclic productsare represented by the formula ##STR10## wherein R and Z have thepreviously states meanings and Y' is the moiety derived by loss of ahydrogen from Y, that is, Y' is imino, alkylimino, oxa or thio. In termsof the preferred reactants of formulas I or II and III, the preferredproducts of formula IV are those wherein Y' is imino and Z is >CH₂ oradjacent Z groups are benzo.

Illustrative of such products are1,5-di(5-hydroxy-2-benzimidazoyl)-3-oxopentane illustratively producedfrom 3,4-diaminophenol and either 4-oxoheptanedioic acid or1,6-dioxaspiro[4.4]nonane-2,7-dione,1,5-di(6-hydroxy-N-methyl-2-benzimidazoyl)-1,2,4,5-dibenzo-3-oxopentaneillustratively produced from 5-hydroxy-2-methylamino-aniline and eitherdi(2-carboxyphenyl) ketone or3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione,1,5-di(5-hydroxy-6-methyl-2-benzothiazoyl)-1,5-dimethyl-3-oxopentaneillustratively produced from 2-amino-4-hydroxy-5-methylthiophenol andeither 2,6-dimethyl-4-oxoheptanedioic acid or3,8-dimethyl-1,6-dioxaspiro[4.4]-nonane-2,7-dione, and1,5-di(5-hydroxy-2-benzoxazoyl)-3-oxopentane produced from4-aminorecorcinol and either dimethyl 4-oxoeptanedioate or1,6-dioxaspiro[4.4]nonane-2,7-dione. Other products will be apparentfrom consideration of the above formulas for the reactants and theheterocyclic bisphenol product.

The heterocyclic bisphenolic products (formula IV) of the invention arearomatic dihydroxy compounds and are precursors of a variety ofpolymeric products obtained by procedures which are conventional forbisphenol compounds. For example, the bisphenola of formula IV arereacted with di(chlorophenyl) sulfone to produce a thermoplastic polymerhaving good properties and dimensional stability at elevatedtemperatures. The products are alternatively employed as precursors ofthermoset resins as by conversion of the bisphenol to the alkali metalsalt by treatment with alkali metal base and reaction of the saltthereby obtained with allyl bromide to produce the bis(allyloxy)derivative which is cured by reaction with conventional curing agents,e.g., a bis(maleimide).

A somewhat special case exists when the hydroxy-substitutedbenzoheterocyclic product of formula IV is produced from ahydroxy-substituted o-phenylenediamine and Y' is therefore imino. Suchproducts are represented by the formula ##STR11## By virtue of theunique relationship of the active hydrogen of each imino group and thecarbonyl group in the 3-position of the five-carbon connecting bridge,dehydration to produce of greater cyclic functionality is possiblewhereas such dehydration cannot occur when Y' is other than iminobecause of the absence of active hydrogens. Such dehydrated products ofhigher cyclic functionality are represented by the formula ##STR12##Such products of formula V are1,2,6,7-di(hydroxybenzimidazo)-1,6-diazaspiro[4.4]nonanes wherein R andZ have the previously stated meanings. By way of specific illustration,the initial product of 3,4-diaminophenol and 4-oxoeptanedioic acid,1,5-di(5-hydroxy-2-benzimidazoyl)-3-oxopentane, undergoes dehydration(cyclization) upon application of heat to produce1,2,6,7-di(5-hydroxybenzimidazo)-1,6-diazaspiro[4.4]nonane of theformula ##STR13## An additional illustrative product of this type is1,2,6,7-di[5-(4-hydroxyphenyl)benzimidazo]-1,6-diazaspiro[4.4]nonaneillustratively produced by heating the initial reaction product from thereaction of 3,4-diamino-4'-hydroxybiphenyl and1,6-dioxaspiro[4.4]nonane-2,7-dione. Other products will be apparentfrom consideration of the formulas for the reactants (formula IVa) andthe product of higher cyclic functionality (formula V).

Conversion to the benzimidazoyl derivatives of formula V is accomplishedby heating the benzimidazoyl derivatives of IVa to a temperature aboveabout 250° C. in a reaction diluent which is the same diluent as that inwhich the benzimidazoyl derivative was produced or which is a differentpolar reaction diluent in which the formula IVa compound is at leastpartially soluble. It is particularly convenient to employ a diluent ormixture of diluents including a diluent with which water forms anazeotrope so that the water formed by the process of dehydrating thebenzimidazoyl derivative to the benzimidazo derivative is easily removedas an azeotrope. Subsequent to the heating/dehydration process thehydroxy-containing hydrocybenzimidazo derivatives (formula V) arerecovered by conventional methods.

The hydroxy-containing benzimidazo derivatives of the invention arebisphenols and as such are useful precursors of polymeric materials ofboth the thermoplastic and thermoset types. Conversion of thesebisphenols to polymeric derivatives is by conventional methods such asare described above. The resulting polymers, in part because of thepolycyclic structure, are characterized by quite high melting points orglass transition temperatures and are particularly useful in hightemperature applications.

The invention is further illustrated by the following IllustrativeEmbodiments which should not be construed as limiting.

Illustrative Embodiment I

When a mixture of 3,4-diaminophenol and 4-oxoheptanedioic acid is heatedin m-cresol, and the resulting mixture is cooled and poured intomethylene chloride, a product will precipitate whose nuclear magneticresonance spectra will be consistent with a product containing1,5-di(5-hydroxy-2-benzimidazoyl)-3-oxopentane.

Illustrative Embodiment II

When the product of Illustrative Embodiment I is heated in toluene untilwater removal is complete, pouring the mixture which results intomethylene chloride will afford a product of high melting point whosenuclear magnetic resonance spectra will be consistent with a productcontaining1,2,6,7-di(5-hydroxy-2-benzimidazoyl)-1,6-diazaspiro[4.4]nonane.

What is claimed is:
 1. The benzoheterocyclic compound of the formula##STR14## wherein R is a hydrocarbyl aromatic group of up to 20 carbonatoms inclusive and one aromatic ring, each R group being attached tothe indicated nitrogens through adjacent aromatic ring carbon atoms ofthe R group, and Z independently is >C(Z')₂ in which Z' independently ishydrogen or methyl.
 2. The compound of claim 1 wherein Z' is hydrogen.3. The compound1,2,6,7-di(5-hydroxy-2-benzimidazo)1,6-diazaspiro[4.4]nonane.